CN106111088A - A kind of preparation method of silicon dioxide/cationic-type polyacrylamide hybrid sorbents - Google Patents
A kind of preparation method of silicon dioxide/cationic-type polyacrylamide hybrid sorbents Download PDFInfo
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- CN106111088A CN106111088A CN201610543296.0A CN201610543296A CN106111088A CN 106111088 A CN106111088 A CN 106111088A CN 201610543296 A CN201610543296 A CN 201610543296A CN 106111088 A CN106111088 A CN 106111088A
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- Prior art keywords
- cationic
- hybrid
- preparation
- silicon dioxide
- sorbents
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002594 sorbent Substances 0.000 title claims abstract description 31
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 25
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 36
- 239000010703 silicon Substances 0.000 claims abstract description 36
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 24
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 125000002091 cationic group Chemical group 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims abstract description 8
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004220 aggregation Methods 0.000 claims abstract description 5
- 230000002776 aggregation Effects 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 125000004423 acyloxy group Chemical group 0.000 claims abstract description 4
- 125000003368 amide group Chemical group 0.000 claims abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- -1 silica anion Chemical class 0.000 claims abstract description 4
- 238000005815 base catalysis Methods 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims abstract 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 27
- 239000012153 distilled water Substances 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 229910002567 K2S2O8 Inorganic materials 0.000 claims description 11
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910052756 noble gas Inorganic materials 0.000 claims description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000006392 deoxygenation reaction Methods 0.000 claims description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 101710194948 Protein phosphatase PhpP Proteins 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 12
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 239000010893 paper waste Substances 0.000 abstract description 7
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 3
- 238000005903 acid hydrolysis reaction Methods 0.000 abstract description 2
- 230000009920 chelation Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides the preparation method of a kind of silicon dioxide/cationic-type polyacrylamide, the method uses the mode of acid hydrolysis base catalysis again that VTES is made the hybrid silicon ball containing vinyl；This hybrid silicon ball is disperseed in aqueous, adds cationic monomer and adsorb at hydridization silicon ball surface；Again under inert gas shielding, add acrylamide and carry out graft copolymerization by solution situ aggregation method, obtain the cationic hybrid sorbents containing amido, acyloxy and silicone hydroxyl.The preparation method of the present invention is simple to operate, environmental protection, containing nitrogen, oxygen atom and silica anion on the strand of this hybrid sorbents, can have excellent absorption property with the calcium ion generation chelation in paper waste and electrostatic adsorption.
Description
Technical field
The invention belongs to field of industrial waste water treatment, be specifically related in paper waste enter rich in the waste water of polyvalent metal ion
The adsorption treatment agent that row processes.
Background technology
Paper manufacturing systems white water system is the important channel that paper industry realizes that cleaning produces.Along with white water system
Improving constantly of degree, Ca in system2+、Mg2+The most constantly accumulating Deng polyvalent metal ion, these metal ions will be with band carboxylic
Base electronegative group combines and unstability, occurs assemble or generate non-ionic stickiness insoluble matter, is that wet end system produces gluing thing
Direct acting factor with deposit.At present, it is used for controlling Ca in paper waste2+And Mg2+Processing method mainly have absorption,
Filtration, ion exchange, precipitation and complexation.Absorption method is as a kind of important Chemical Physics method, universal in water treatment procedure
Use, and the selection of adsorbing material and development are one of key factors of absorption method process paper waste.
The adsorbent mainly design being used at present processing paper waste can organic with metal ion generation complexing
Macromolecule.China's papermaking journal 2,009 24 (1) and 2,012 27 (4) describes respectively and utilizes carboxylic modified natural polymer
ACS and amphiphilic polymers P (AM-DMDAAC-AA) processes Ca2+, the wherein carboxyl energy on strand and Ca2+Occur complexation anti-
Answer thus reach absorption, the purpose of removal metal ion.Both organic polymers are to Ca2+Adsorption effect general, adsorbance
Undesirable, carboxyl-content relatively low on its strand limits Ca in paper waste2+Complexing, cause adsorbance relatively
Low.And Inorganic-Organic Hybrid Material is used as adsorbent and has become the study hotspot in water-treatment technology field.New Chemical Materials
201240 (2) utilize sulfomethylation improved silica/polyacrylamide (SiO2/ PAM) composite adsorption resin adsorb a huge sum of money
Belonging to ion Pb and Cu, its adsorption capacity and adsorption rate are all greatly improved, and achieve good adsorption effect.Therefore develop new
Type inorganic-organic hybridization adsorbent, improves the adsorption capacity to paper making wet part polyvalent metal ion, significant.
Summary of the invention
For problem present in background technology, it is an object of the invention to provide a kind of silicon dioxide/cationic poly third
The preparation method of acrylamide hybrid sorbents, contain in this sorbent molecule can be with calcium metal ion (Ca simultaneously2+) chelate
The N of effect, O atom, and and Ca2+There is the silicone hydroxyl anion (Si-O of Electrostatic Absorption-), therefore substantially increase Ca2+
Adsorbance.
The technical solution that the present invention uses is: use the mode of acid hydrolysis base catalysis again by vinyl triethoxyl silicon
Alkane (VTES) makes the hybrid silicon ball containing vinyl；This hybrid silicon ball is disperseed in aqueous, adds cationic monomer and inhale
It is attached to hydridization silicon ball surface；Again under inert gas shielding, add acrylamide and carry out grafting altogether by solution-situ aggregation method
Poly-, obtain the cationic hybrid sorbents containing amido, acyloxy and silicone hydroxyl.
The preparation method of the silicon dioxide of the present invention/cationic-type polyacrylamide hybrid sorbents, comprises the following steps:
(1) preparation containing vinyl hybrid silicon ball: be placed in 0.9～4.5gVTES in the flask equipped with 50mL distilled water,
Solution ph in flask is adjusted to 3～4 by acid adding, makes VTES hydrolysis 70～120min；Add the ammonia that mass concentration is 25%
It is 9.5～12 that liquid in flask is adjusted to pH value, carries out base catalyzed condensation reaction 1.5～3h, is centrifuged separating 10 by product
～20min (2000～3000rpm), take lower sediment and be dried, obtain the hybrid silicon ball containing vinyl, grasp for next step
Make.
Described acid is mineral acid or organic acid, specially the one in hydrochloric acid, nitric acid, sulphuric acid, acid or glacial acetic acid.
(2) use solution-situ aggregation method to prepare hybrid sorbents, and prepare polyreaction mixture by formula as below
System:
Step (1) gained hybrid silicon ball, the acrylamide (AM) of 1/3rd mass and cationic monomer are placed in equipped with
In the container of distilled water, ultrasonic disperse 5～10min, it is filled with noble gas deoxygenation 15～30min, adds chelating agen and reduction
Property initiator, bath temperature is increased to 60 DEG C, instills residue AM monomer and oxidized form initiator solution, time for adding be about 30～
40min, and reaction 6～10h at this temperature, obtain transparent yellow solution.Product dehydrated alcohol cyclic washing, mistake
Filter, normal-temperature vacuum is dried to constant weight, obtains silicon dioxide/cationic-type polyacrylamide hybrid sorbents.
Described cationic monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) and acrylyl oxy-ethyl-trimethyl
One in ammonium chloride (DAC), wherein DAC is preferred.
Described initiator is for comprising NaHSO3、K2S2O8With the composite initiator of AIBA 2HCl, wherein NaHSO3For reduction
Type initiator, K2S2O8Being oxidized form initiator with AIBA 2HCl, the concentration of oxidized form initiator solution is 0.1～0.3%,
AIBA 2HCl accounts for the 15～50% of initiator gross mass, NaHSO3And K2S2O8Mol ratio be 1:2.
Described chelating agen is the one in EDTA, DTPA, NTA or STPP.
Described noble gas is nitrogen.
The method comprises the steps of firstly, preparing containing vinyl hybrid silicon ball, the vinyl of its microsphere surface can occur poly-with vinyl monomer
Close reaction, hybrid silicon ball can occur the ionization of silicone hydroxyl under the conditions of neutral and alkali simultaneously, is allowed to surface electronegative, can with sun from
Sub-monomer generation Electrostatic Absorption, the graft copolymerization for hybrid silicon ball and vinyl monomer creates favorable conditions, and is formed with hydridization
Silicon ball is the branching shape molecular structure of junction point, and in molecule containing amide groups, acyloxy and silicone hydroxyl silicon dioxide/sun from
Subtype polyacrylamide hybrid sorbents.
The beneficial effects of the present invention is:
(1) using the hybrid silicon ball containing vinyl is raw material, and diameter of particle is little, and specific surface area is big, and microparticle surfaces contains rich
Rich silicone hydroxyl, the most electronegative, can improve inhale with the polyvalent metal ion generation Electrostatic Absorption in paper waste
Attached effect and adsorbance.
(2) vinyl double bond is contained on the surface containing vinyl hybrid silicon ball, with vinyl monomer generation graft copolymerization, is formed
The hybrid sorbents of branching shape structure, contained N in its molecular structure, O atom can be with metal Ca2+There is intramolecular chelating, its
Interatomic spacing is short, and chelation is easier to occur, and acts on more firm.
(3) the hybrid silicon ball Han vinyl is combined on nanoscale with organic polymer chain, there is covalent bond and connects,
Grafting efficiency is high.
(4) in preparation process, solvent for use is water, low cost, and environmental pollution is little.
Accompanying drawing explanation
Below in conjunction with the accompanying drawings this experiment is further illustrated.
Fig. 1 is the response path schematic diagram of silicon dioxide/cationic-type polyacrylamide hybrid sorbents.
Fig. 2 is hybrid silicon ball (a) and silicon dioxide/cationic-type polyacrylamide hybrid sorbents (b) in embodiment one
Infrared spectrum.
Fig. 3 is that in embodiment one, the scanning electron microscope (SEM) photograph (a) of hybrid silicon ball and silicon dioxide/cationic-type polyacrylamide are miscellaneous
Change the transmission electron microscope picture (b) of adsorbent.
Detailed description of the invention
Presently in connection with specific embodiment, the invention will be further described, and following example are intended to illustrate rather than
Limitation of the invention further.
Embodiment one:
(1) preparation containing vinyl hybrid silicon ball: 0.9g VTES is put in the flask equipped with 50mL distilled water, use salt
Solution ph in flask is adjusted to 3.20 by acid solution, makes VTES hydrolyze 90min；Add 0.6mL mass concentration be 25% dense
Ammonia, in flask, liquid pH value is 9.95, carries out base catalyzed condensation reaction 2h, product is centrifuged (2000rpm) and separates
10min, takes lower sediment and is dried, obtain particle diameter be 500nm containing vinyl hybrid silicon ball.
(2) preparation of silicon dioxide/cationic-type polyacrylamide hybrid sorbents: by 0.0391g hybrid silicon ball,
2.2805g AM and 1.1427g DAC is placed in the container equipped with 15mL distilled water, and ultrasonic disperse 5min is filled with noble gas and removes
Oxygen 20min, adds 0.0015g EDTA and 0.0025g NaHSO3, bath temperature is increased to 60 DEG C, is stirred at reflux, drips respectively
Enter to remain AM monomer (4.5610g AM is dissolved in 15mL distilled water) and oxidized form initiator solution (0.0128g K2S2O8With
0.0082g AIBA 2HCl is dissolved in 20mL distilled water), time for adding is about 30min, and reacts 8h at this temperature,
To transparent yellow solution.Reactant dehydrated alcohol cyclic washing, filters, and normal-temperature vacuum is dried to constant weight, obtains titanium dioxide
Silicon/cationic-type polyacrylamide hybrid sorbents.When ionic calcium soln pH value is 10.0, calcium ion adsorbance is reached by product
To 166.0mg/g.
Embodiment two:
(1) preparation containing vinyl hybrid silicon ball: 2.7gVTES is put in the flask equipped with 50mL distilled water, use hydrochloric acid
Solution ph in flask is adjusted to 3.29 by solution, makes VTES hydrolyze 90min；Add the dense ammonia that 0.6mL mass concentration is 25%
Water, in flask, liquid pH value is 9.95, carries out base catalyzed condensation reaction 2.5h, product is centrifuged (3000rpm) and separates
8min, takes lower sediment and is dried, obtain particle diameter be 625nm containing vinyl hybrid silicon ball.
(2) preparation of silicon dioxide/cationic-type polyacrylamide hybrid sorbents: by 0.0435g hybrid silicon ball,
2.3892g AM and 1.7774g DAC is placed in the container equipped with 15mL distilled water, and ultrasonic disperse 5min is filled with noble gas and removes
Oxygen 20min, adds 0.0020g EDTA and 0.0031g NaHSO3, bath temperature is increased to 60 DEG C, is stirred at reflux, drips respectively
Enter to remain AM monomer (4.7784g AM is dissolved in 15mL distilled water) and oxidized form initiator solution (0.0157g K2S2O8With
0.0189g AIBA 2HCl is dissolved in 20mL distilled water), time for adding is about 30min, and reacts 6h at this temperature,
To transparent yellow solution.Reactant dehydrated alcohol cyclic washing, filters, and normal-temperature vacuum is dried to constant weight, obtains titanium dioxide
Silicon/cationic-type polyacrylamide hybrid sorbents.When ionic calcium soln pH value is 10.0, calcium ion adsorbance is reached by product
To 225.2mg/g.
Embodiment three:
(1) preparation containing vinyl hybrid silicon ball: 2.7gVTES is put in the flask equipped with 50mL distilled water, use hydrochloric acid
Solution ph in flask is adjusted to 3.29 by solution, makes VTES hydrolyze 90min；Add the dense ammonia that 1.0mL mass concentration is 25%
Water, in flask, liquid pH value is 10.05, carries out base catalyzed condensation reaction 3h, product is centrifuged (2000rpm) and separates
10min, takes lower sediment and is dried, obtain particle diameter be 500nm containing vinyl hybrid silicon ball.
(2) preparation of silicon dioxide/cationic-type polyacrylamide hybrid sorbents: by 0.0608g hybrid silicon ball,
2.3892g AM and 1.7774g DAC is placed in the container equipped with 15mL distilled water, and ultrasonic disperse 5min is filled with noble gas and removes
Oxygen 20min, adds 0.0010g EDTA and 0.0063g NaHSO3, bath temperature is increased to 60 DEG C, is stirred at reflux, drips respectively
Enter to remain AM monomer (4.7784g AM is dissolved in 15mL distilled water) and oxidized form initiator solution (0.0329g K2S2O8With
0.0131g AIBA 2HCl is dissolved in 20mL distilled water), time for adding is about 33min, and reacts 6h at this temperature,
To transparent yellow solution.Reactant dehydrated alcohol cyclic washing, filters, and normal-temperature vacuum is dried to constant weight, obtains titanium dioxide
Silicon/cationic-type polyacrylamide hybrid sorbents.When ionic calcium soln pH value is 10.0, calcium ion adsorbance is reached by product
To 228.8mg/g.
Embodiment four:
(1) preparation containing vinyl hybrid silicon ball: 2.7gVTES is put in the flask equipped with 50mL distilled water, use hydrochloric acid
Solution ph in flask is adjusted to 3.40 by solution, makes VTES hydrolyze 90min；Add the dense ammonia that 0.6mL mass concentration is 25%
Water, in flask, liquid pH value is 9.95, carries out base catalyzed condensation reaction 2h, product is centrifuged (2000rpm) and separates
10min, takes lower sediment and is dried, obtain particle diameter be 625nm containing vinyl hybrid silicon ball.
(2) preparation of silicon dioxide/cationic-type polyacrylamide hybrid sorbents: by 0.0391g hybrid silicon ball,
2.2805g AM and 1.1400g DAC is placed in the container equipped with 15mL distilled water, and ultrasonic disperse 5min is filled with noble gas and removes
Oxygen 20min, adds 0.0020g EDTA and 0.0019g NaHSO3, bath temperature is increased to 60 DEG C, is stirred at reflux, drips respectively
Enter to remain AM monomer (4.561g AM is dissolved in 15mL distilled water) and oxidized form initiator solution (0.0098g K2S2O8With
0.0117g AIBA 2HCl is dissolved in 20mL distilled water), time for adding is about 35min, and reacts 8h at this temperature,
To transparent yellow solution.Reactant dehydrated alcohol cyclic washing, filters, and normal-temperature vacuum is dried to constant weight, obtains titanium dioxide
Silicon/cationic-type polyacrylamide hybrid sorbents.When ionic calcium soln pH value is 10.0, calcium ion adsorbance is reached by product
To 233.6mg/g.
Comparative example one:
The preparation of cationic-type polyacrylamide adsorbent: 2.2808g AM and 0.3809g DAC is placed in equipped with 8.3mL
In the container of distilled water, ultrasonic disperse 5min, it is filled with noble gas deoxygenation 30min, adds 0.0015g EDTA and 0.0047g
NaHSO3, bath temperature is increased to 40 DEG C, is stirred at reflux, be respectively dropped into residue AM and DAC monomer (4.5617g AM and
0.7618g DAC is dissolved in 16.6mL distilled water) and oxidized form initiator solution (0.0246g K2S2O8With 0.0098g
AIBA 2HCl is dissolved in 20mL distilled water), time for adding is about 30min, temperature is risen at this temperature after reaction 2h
65 DEG C are continued reaction 4h, obtain transparent yellow solution.Reactant dehydrated alcohol cyclic washing, filters, and normal-temperature vacuum is done
Dry to constant weight, obtain cationic-type polyacrylamide adsorbent.When ionic calcium soln pH value is 10.0, calcium ion is adsorbed by product
Amount reaches 92.8mg/g.
Claims (7)
1. the preparation method of silicon dioxide/cationic-type polyacrylamide hybrid sorbents, it is characterised in that: use sour water
VTES is made the hybrid silicon ball containing vinyl by the mode of solution base catalysis again；This hybrid silicon ball is dispersed in
In aqueous solution, add cationic monomer and adsorb at hydridization silicon ball surface；Again under inert gas shielding, add acrylamide and lead to
Cross solution-situ aggregation method and carry out graft copolymerization, obtain the cationic hydridization absorption containing amido, acyloxy and silicone hydroxyl
Agent.
The preparation method of a kind of silicon dioxide/cationic-type polyacrylamide hybrid sorbents the most according to claim 1,
It is characterized in that this preparation method comprises the following steps:
(1) preparation containing vinyl hybrid silicon ball: 0.9～4.5g VTES is placed in the flask equipped with 50mL distilled water, acid adding
Solution ph in flask is adjusted to 3～4, makes VTES hydrolysis 70～120min；Add the ammonia that mass concentration is 25% will burn
In bottle, to be adjusted to pH value be 9.5～12 to liquid, carries out base catalyzed condensation reaction 1.5～3h, be centrifuged product separating 10～
20min (2000～3000rpm), takes lower sediment and is dried, and obtains the hybrid silicon ball containing vinyl, grasps for next step
Make.
(2) solution-situ aggregation method is used to prepare hybrid sorbents, and by formula as below preparation polyreaction mixed system:
Step (1) gained hybrid silicon ball, the acrylamide (AM) of 1/3rd mass and cationic monomer are placed in equipped with distillation
In the container of water, ultrasonic disperse 5～10min, it is filled with noble gas deoxygenation 15～30min, adds chelating agen and reproducibility is drawn
Sending out agent, bath temperature is increased to 60 DEG C, instills residue AM monomer and oxidized form initiator solution, time for adding be about 30～
40min, and reaction 6～10h at this temperature, obtain transparent yellow solution.Product dehydrated alcohol cyclic washing, mistake
Filter, normal-temperature vacuum is dried to constant weight, obtains silicon dioxide/cationic-type polyacrylamide hybrid sorbents.
The preparation method of a kind of silicon dioxide/cationic-type polyacrylamide hybrid sorbents the most as claimed in claim 2, its
It is characterised by: acid described in step (1) is in mineral acid or organic acid, specially hydrochloric acid, nitric acid, sulphuric acid, acid or glacial acetic acid
A kind of.
The preparation method of a kind of silicon dioxide/cationic-type polyacrylamide hybrid sorbents the most as claimed in claim 2, its
It is characterised by: cationic monomer described in step (2) is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) and acryloyl-oxy
One in ethyl-trimethyl salmiac (DAC), wherein DAC is preferred.
The preparation method of a kind of silicon dioxide/cationic-type polyacrylamide hybrid sorbents the most as claimed in claim 2, its
It is characterised by: described in step (2), initiator is for comprising NaHSO3、K2S2O8With the composite initiator of AIBA 2HCl, wherein
NaHSO3For reduced form initiator, K2S2O8Being oxidized form initiator with AIBA 2HCl, the concentration of oxidized form initiator solution is
0.1～0.3%, AIBA 2HCl accounts for the 15～50% of initiator gross mass, NaHSO3And K2S2O8Mol ratio be 1:2.
The preparation method of a kind of silicon dioxide/cationic-type polyacrylamide hybrid sorbents the most as claimed in claim 2, its
It is characterised by: described in step (2), chelating agen is the one in EDTA, DTPA, NTA or STPP.
The preparation method of a kind of silicon dioxide/cationic-type polyacrylamide hybrid sorbents the most as claimed in claim 2, its
It is characterised by: described in step (2), noble gas is nitrogen.
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